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Abstract:

The invention provides a process for direct liquification of cellulosic
biomass, which may be used to liquefy all of the organics in cellulosic
biomass, including all high molecular polymeric components such as
carbohydrates and lignins, into small molecular organics in a short time
under mild conditions. In other words, there is provided a technology
capable of converting cellulosic biomass into oil. The resultant
renewable high-quality oil may be converted into liquid fuels such as
gasoline etc., or used as starting materials in chemical engineering
industry. The technology for direct liquification of cellulosic biomass
as disclosed in the invention is the first one-step process in the world
for direct liquification of cellulosic biomass without black tar
formation and gasification.

Claims:

1. A process for direct liquification of cellulosic biomass, comprising:
(a) providing a mixture comprising cellulosic biomass, a catalyst and an
optional polar solvent; wherein the catalyst is selected from the group
consisting of: (i) a first catalyst which is an alkaline substance and
includes alkali metal hydroxides, alkaline earth metal hydroxides, alkali
metal oxides, alkaline earth metal oxides, alkali metal carbonates, or
alkaline earth metal carbonates; and/or (ii) a second catalyst including
transition metal oxides, transition metal sulfides, bimetallic salts of
transition metals, anthraquinone and its derivatives, or demethylated
lignin; and/or (iii) a combined catalyst of a first catalyst and a second
catalyst; with the proviso that the mixture may comprise no polar solvent
when cellulosic biomass contributes greater than 6% (w/w) of the water
content in the mixture; (b) directly liquefying the mixture under
liquification conditions to obtain liquification products.

2. The process of claim 1, wherein step (a) comprises mixing the
cellulosic biomass and the polar solvent first and then forming the
mixture by adding the catalyst.

3. The process of claim 1, wherein step (b) is carried out in a pressure
reactor.

4. The process of claim 1, wherein the cellulosic biomass includes but is
not limited to fresh cellulosic biomass or dry cellulosic biomass.

5. The process of claim 1, wherein: the solvent includes hydroxyl
compounds, substances which can be converted into hydroxyl compounds
under alkaline conditions, ion liquids and water or combinations thereof;
the hydroxyl compounds include all alcohol solvents and phenol solvents;
the substances which can be converted into hydroxyl compounds under
alkaline conditions include but are not limited to acetone, methyl ethyl
ketone, benzaldehyde.

7. The process of claim 1, wherein the catalyst is a combined catalyst of
a first catalyst and a second catalyst.

8. The process of claim 1, wherein: in the mixture, the content of the
first catalyst is 0.1%-100% of the dry weight of the cellulosic biomass,
and/or the content of the second catalyst is 0.01%-100% of the dry weight
of the cellulosic biomass.

9. The process of claim 1, wherein the liquification conditions include:
(1) in step (b), the liquification reactions may take place in the
presence of oxygen; preferably, the liquification reactions take place in
the presence of an inert gas, carbon monoxide or hydrogen; (2) in step
(b), hydrogen is used, and the initial pressure of hydrogen is 2-300
atmospheres.

Description:

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application is a 35 U.S.C. 371 national stage application of
International Application No. PCT/CN2008/071775, filed Jul. 28, 2008, the
entire contents of which is incorporated herein by reference.

TECHNICAL FIELD

[0002] The invention relates to the field of refining cellulosic biomass,
particularly to a process for direct liquification of cellulosic biomass.

BACKGROUND

[0003] Nowadays, human beings see the most critical turning point in
history when the consumption of nonrenewable fossil energies such as
coal, oil, natural gas, etc., grows rapidly. The reason lies in not only
the possible crisis of energy shortage, but also the global warming
caused by the huge amount of fossil-energy-derived carbon dioxide. It is
widely accepted that global warming is the very origin of the global
disastrous weather phenomena in recent years. In order to ensure the
survival and sustainable development of human beings, new and renewable
energy resources have to be developed and utilized.

[0004] On the other hand, since most starting materials in modern chemical
engineering industry originate from oil, reduction of the emission of the
green house gas, carbon dioxide, necessitates less use of oil as the
liquid fuel. At the same time, modern chemical engineering industry
requires maximum use of renewable starting materials in place of oil as
the starting material.

[0005] Cellulosic biomass contains a large quantity of linear organics and
a multiple of aromatic compounds and is thus a renewable energy resource
material with rich sources. As evaluated by a UN expert panel, only
cellulosic biomass, as a renewable energy resource, is capable of
supporting the survival and development of human beings. A fatal drawback
of cellulosic biomass is its density that is too low. Before it can be
used as a renewable biological energy resource, a problem that has to be
addressed is the production of high-energy-density products by refining
cellulosic biomass.

[0006] One solution is liquification of cellulosic biomass. After
liquification of cellulose, a plurality of small organic compounds may be
obtained. These small organic compounds are good starting materials for
both liquid fuels and modern chemical engineering industry.

[0007] PCT/CN2006/000120 discloses a production method for refining
cellulosic biomass, according to which it may be expected that the cost
of producing fuel ethanol from cellulosic biomass on a commercial scale
will be comparable to that from starch. However, this method involves
several steps, so that the process is still complex, and the production
cost is still high.

[0008] Thus, there remains an urgent need in the art for an efficient
process for direct liquification of cellulosic biomass with simple
procedures. However, there is no report so far on direct liquification of
cellulosic biomass.

SUMMARY OF THE INVENTION

[0009] The object of the invention is to provide a simple and efficient
process for direct liquification of cellulosic biomass.

[0010] According to the first aspect of the invention, there is provided a
process for direct liquification of cellulosic biomass, comprising:

[0015] (iii) a combined catalyst of a first catalyst and a second
catalyst; with the proviso that the mixture may comprise no polar solvent
when cellulosic biomass contributes greater than 6% of the water content
in the mixture;

[0025] In another preferred embodiment, the solvent includes hydroxyl
compounds, substances which can be converted into hydroxyl compounds
under alkaline conditions, ion liquids and water or combinations thereof.

[0026] The hydroxyl compounds include all alcohol solvents and phenol
solvents.

[0027] In another preferred embodiment, the alcohol solvents include but
are not limited to carbon alcohols, mercaptons, silanols, with carbon
alcohols preferred. Among all carbon alcohols, small molecular alcohols,
such as methanol, ethanol, propanol, ethylene glycol, glycerin, butanol
are preferred.

[0028] In another preferred embodiment, the phenol solvents include but
are not limited to phenol, monomethyl phenol, dimethyl phenol, trimethyl
phenol, methoxyl phenol, with phenol preferred.

[0029] In another preferred embodiment, the substances which can be
converted into hydroxyl compounds under alkaline conditions include but
are not limited to ketones and aldehydes, including but not limited to
acetone, methyl ethyl ketone, benzaldehyde.

[0038] The bimetallic salts of transition metals include but are not
limited to copper chromite (Cu2Cr2O5), iron chromite or a
combination thereof.

[0039] In another preferred embodiment, the catalyst is a combined
catalyst consisting of a first catalyst and a second catalyst.

[0040] In another preferred embodiment, in the mixture, the content of the
first catalyst is 0.1%-100% of the dry weight of the cellulosic biomass,
and or the content of the second catalyst is 0.01%-100% of the dry weight
of the cellulosic biomass.

[0041] In another preferred embodiment, the liquification conditions
include:

[0042] (1) in step (b), the liquification reactions may take place in the
presence of oxygen;

[0043] Preferably, the liquification reactions take place in the presence
of an inert gas, carbon monoxide or hydrogen;

[0044] (2) in step (b), hydrogen is used, and the initial pressure of
hydrogen is 2-300 atmospheres;

[0046] FIG. 1 shows the result of GC/MS analysis for the direct
liquification products of cow dung, wherein the horizontal coordinate
represents retention time in minute, and the vertical coordinate
represents relative abundance.

DETAILED DESCRIPTION OF THE APPLICATION

[0047] After extensive and intensive study, the inventors have found that
in the presence of a particular catalyst, cellulosic biomass may be
directly liquefied in a short time under mild conditions. Based on this
finding, the invention has been fulfilled.

[0048] In particular, the invention provides a process for direct
liquification of cellulosic biomass. The process can be used to convert
most (or all) of the organics in cellulosic biomass into small molecular
organic compounds in a short time under mild conditions, while avoiding
serious loss of organic carbon caused by carbonization of the organics in
cellulosic biomass (into inorganics) or gasification of the organics in
cellulosic biomass (into small molecular gases, such as methane, ethane,
propane, carbon monoxide, carbon dioxide, etc.).

[0050] The process for direct liquification of cellulosic biomass as
disclosed in the invention is suitable for all kinds of biomass
containing cellulose, including but not limited to fresh cellulosic
biomass or dried cellulosic biomass (as described above).

[0051] In one embodiment of the invention, the polar solvent includes
hydroxyl compounds, substances which can be converted into hydroxyl
compounds under alkaline conditions, ion liquids and water. The hydroxyl
compounds include all alcohol solvents and phenol solvents, such as
carbon alcohols, mercaptons, silanols, with carbon alcohols preferred.
Among all carbon alcohols, small molecular alcohols, such as methanol,
ethanol, propanol, ethylene glycol, glycerin, butanol are preferred.
Among the phenol compounds, for example, phenol, monomethyl phenol,
dimethyl phenol, trimethyl phenol, methoxyl phenol, etc., phenol is
preferred. The substances which can be converted into hydroxyl compounds
under alkaline conditions include ketones and aldehydes, such as acetone,
methyl ethyl ketone, benzaldehyde, etc. The ionic liquids include all
liquids composed of organic cations containing nitrogen, phosphorus and
large inorganic anions, wherein cations are, for example, alkyl ammonium
salts, alkyl phosphate salts, N-alkyl pyridine and N,N'-dialkylimidazole
cations, anions are, for example, halogen ions, AlCl4.sup.-, and
multiple ions containing fluorine, phosphorus, sulfur, such as
BF4.sup.-, PF6.sup.-, CF3SO3.sup.-. Any of these
polar solvents may be used alone or in combination.

[0052] In one embodiment of the invention, cellulosic biomass may be used
in crushed form without addition of any polar solvent if the cellulosic
biomass contains more than 6% of water. If cellulosic biomass is dry
substance without water, a polar solvent is typically used in an amount
of no less than 10% (weight/volume) of the cellulosic biomass.

[0056] Each of the first catalyst and the second catalyst may be used
alone. Preferably, the first catalyst and the second catalyst may be used
together. The adducts formed by forming various non-covalent bonds
between the substance of the first catalyst and that of the second
catalyst, as well as between those of the second catalyst, may function
the same.

[0057] Generally, the amount of the first catalyst used is 0.1%-100% of
the (dry) weight of the cellulosic biomass. Otherwise, although the
catalytic reactions may also occur, they will be slow if the amount of
the first catalyst is lower than the above range, or the cost will be too
high if that amount is higher than the above range. Neither of the cases
is preferred.

[0058] When the first catalyst and the second catalyst are used together,
the mixing ratio of them is not particularly limited. Generally, the
weight ratio of the first catalyst to the second catalyst may be, for
example, 0.01-99.9 to 99.9-0.01.

[0059] Liquification reactions may be carried out in the presence of
oxygen. However, the reactions are most preferably carried out in the
absence of oxygen or in the presence of an inert gas, carbon monoxide or
hydrogen, because the products of direct liquification of cellulosic
biomass comprise a large quantity of single-ring phenols as well as
intermediate products of hydrolyzation of cellulose and semicellulose,
and some of the second catalysts are ready to be oxidized, leading to
complex products, gasification of cellulosic biomass and deactivation of
catalyst.

[0060] Since hydrogen is expensive than an inert gas, when hydrogen is
used in the reactions, oxygen in the reactions is generally removed by
replacement with an inert gas, and then hydrogen is filled to carry out
the reactions. The initial pressure of hydrogen is generally in the range
of 2-300 atmospheres. Otherwise, although the reactions may also occur,
they will be slow if the amount of hydrogen used is lower than the above
range, or the cost will be too high while a portion of the single-ring
phenol products will be reduced if the amount of hydrogen used is higher
than the above range. Neither of the cases is preferred.

[0061] The reaction temperature used is generally in the range of
50-600° C. Otherwise, although the reactions may also occur
successfully, they will be slow if the temperature is lower than the
above range, or the cost will be too high while a portion of the
cellulosic biomass will be carbonized or gasified, leading to a reduced
yield, if the temperature is higher than the above range. Neither of the
cases is preferred. Preferably, the temperature is 100-500° C.
More preferably, the temperature is 150-400° C.

[0062] In the one-step process for direct liquification of cellulosic
biomass as disclosed by the invention, either unpretreated or pretreated
cellulosic biomass may be used. The use of unpretreated cellulosic
biomass may reduce the cost for refining cellulosic biomass
significantly. However, scrap produced in many existing production
processes may be regarded as pretreated material, for example, bagasse
produced in sugar milling, etc. The direct liquification reactions of
pretreated cellulosic biomass may still proceed very well.

[0063] None of the existing processes for pretreating cellulosic biomass
has any impact on the technology and production process for one-step
direct liquification of biomass according to the invention.

[0064] The process for direct liquification of cellulosic biomass as
disclosed in the invention may be carried out in a batch reactor system,
a continuous flow reactor system or a continuous flow-through reactor
system.

[0065] The main advantages of the invention include:

[0066] (a) Most (or all) of the components of the cellulosic biomass may
be liquefied in a single step with substantially no carbonization or
gasification according to the one-step process for direct liquification
of cellulosic biomass.

[0067] (b) The process of the invention shortens the time for generation
of oil from tens of millions of years to a dozen minutes or up to several
hours, and the resultant liquefied products are of very high quantity,
with substantially no heavy metals and extremely low contents of sulfur
and nitrogen (mainly derived from proteins in cellulosic biomass), and
may be converted into liquid fuels such as gasoline (and thus used as
artificial renewable oil products) or used as starting materials in
chemical engineering industry.

EXAMPLES

[0068] The following embodiments are provided to make better illustration
of the invention and not intended to limit the content as disclosed in
the invention thereto. Unless otherwise indicated specifically, all
percentages are based on weight.

[0069] The reaction products were analyzed using chromatography, such as
chromatography-mass spectrum.

Example 1

Direct Liquification of Cow Dunq

[0070] Into a 100 mL stainless autoclave were added 5 g naturally dried
solid cow dung particles (water content: 6.0%), 0.4 g iron sulfide and 50
g phenol. The mixture was heated to 80° C., and deoxygenated twice
with nitrogen under agitation. The reaction system was filled with
hydrogen to 100 atmospheres (10 MPa), sealed and then heated to
300° C. After held for 5 hours, the system was cooled to room
temperature. The pressure was only lowered by about 5 atmospheres. After
the gas was expelled, the liquid products were poured out, and the
autoclave was washed twice with a little toluene. No indication of
carbonization reaction was found in the autoclave.

[0071] Analysis of the resultant liquid products showed that the main
organic components were single-ring aromatic compounds. Further analysis
indicated, as shown by the analysis result in FIG. 1, that among the
single-ring compounds which had a weight content of over 3% were methyl
phenol (m/e=108), dimethyl phenol (m/e=122), trimethyl phenol (m/e=136),
ethyl phenol (m/e=122), methoxyl phenol (m/e=124), isopropyl phenol
(m/e=136), methoxyl methyl phenol (m/e=138), vanillin (m/e=152), with
some organics at relatively lower contents. The yield of small molecular
organic compounds after liquification was 92.7%.

Example 2

Liquification of Pretreated Wheat Straw

[0072] Step 1: Pretreatment

[0073] Into an appropriate vessel were added 30.0 g crushed and naturally
dried wheat straw (water content: 5.8%) and 100 mL purified water. The
mixture was heated to near 100° C. under agitation and held for
about 10 minutes. Then the resultant dark brown yellow liquid was
filtered off (dewaxing), and the remaining solid was vacuum dried and
then loaded into a corrosion-resistant reactor into which 150 mL water
containing 1% sulfuric acid was then added. The temperature was raised to
120° C. After agitation for 60 minutes at this temperature, the
system was cooled to room temperature. The solution of mixed sugar of
hemicellulose was filtered off, and the solid products were washed with
deionized water to neutral and vacuum dried for later use.

Step 2: Liquification

[0074] Into a 200 mL stainless autoclave were added 10 g of the solid
products containing cellulose, lignin and a little ash (inherently
contained in stalk) as obtained in step 1, 8 g sodium hydroxide, 10 mg
anthraquinone and 90 mL water. After the mixture was deoxygenated twice
with nitrogen under agitation, the reaction system was filled with
hydrogen to 40 atmospheres (4 MPa), sealed and heated to 200° C.
After held for 2 hours, the system was cooled to room temperature. The
pressure was only lowered by 2-3 atmospheres. After the gas was expelled,
the liquid products were filtered, and the autoclave was washed twice
with a little 1% aqueous solution of sodium hydroxide. No indication of
carbonization reaction was found in the autoclave. After the washing
liquid was filtered, the filler residue was washed twice with a little 1%
aqueous solution of sodium hydroxide and then vacuum dried. Analysis
indicated that neither organic nor elemental carbon was present in the
filter residue.

[0075] Analysis of the resultant liquid products showed that the main
organic components were single-ring aromatic compounds, multihydroxyl
compounds containing 6 carbons and a small amount of water-soluble
polysaccharides. Further analysis indicated that among the single-ring
compounds which had a weight content of over 3% were phenol (m/e=94),
methyl phenol (m/e=108), dimethyl phenol (m/e=122), trimethyl phenol
(m/e=136), ethyl phenol (m/e=122), methoxyl phenol (m/e=124), isopropyl
phenol (m/e=136), methoxyl methyl phenol (m/e=138), vanillin (m/e=152),
with some organics at relatively lower contents. The multihydroxyl
compounds containing 6 carbons were mainly a variety of isomeric organics
having molecular weights of m/e=196, m/e=182, m/e=166. With the aromatic
compounds and the multihydroxyl compounds considered together, the yield
of small molecular organic compounds after liquification was 96.5%.

[0076] The results show that pretreated cellulosic biomass is quite ready
to be liquefied into small molecular organics without carbonization or
gasification under the conditions as disclosed in the invention.

Example 3

Direct Liquification of Wheat Straw (Unpretreated Wheat Straw)

[0077] Into a 200 mL stainless autoclave were added 10 g naturally dried
solid wheat straw particles which had been crushed to about 2 mm (water
content: 5.8%), 8 g sodium hydroxide, 10 mg anthraquinone and 90 mL
water. After the mixture was deoxygenated twice with nitrogen under
agitation, the reaction system was filled with hydrogen to 40 atmospheres
(4 MPa), sealed and heated to 200° C. After held for 2 hours, the
system was cooled to room temperature. The pressure was only lowered by
2-3 atmospheres. After the gas was expelled, the liquid products were
filtered, and the autoclave was washed twice with a little 1% aqueous
solution of sodium hydroxide. No indication of carbonization reaction was
found in the autoclave. After the washing liquid was filtered, the filler
residue was washed twice with a little 1% aqueous solution of sodium
hydroxide and then vacuum dried. Analysis indicated that neither organic
nor elemental carbon was present in the filter residue.

[0078] Analysis of the resultant liquid products showed that the main
organic components were single-ring aromatic compounds, multihydroxyl
compounds containing 5 and 6 carbons, and a small amount of water-soluble
polysaccharides. Further analysis indicated that among the single-ring
compounds which had a weight content of over 3% were phenol (m/e=94),
methyl phenol (m/e=108), dimethyl phenol (m/e=122), trimethyl phenol
(m/e=136), ethyl phenol (m/e=122), methoxyl phenol (m/e=124), isopropyl
phenol (m/e=136), methoxyl methyl phenol (m/e=138), vanillin (m/e=152),
with some organics at relatively lower contents. The multihydroxyl
compounds containing 5 and 6 carbons were mainly a variety of isomeric
organics having molecular weights of m/e=196, m/e=182, m/e=166, m/e=152,
m/e=136. With the aromatic compounds and the multihydroxyl compounds
considered together, the yield of small molecular organic compounds after
liquification was 94.8%.

[0079] The results show that the liquification reactions of unpretreated
cellulosic biomass are not impacted, and the distribution of the products
is quite similar to that for pretreated stalk, except for several
additional products derived from five-carbon saccharides.

Example 4

Direct Liquification of Rape Stalk

[0080] Into a 200 mL stainless autoclave were added 10 g naturally dried
solid rape stalk particles which had been crushed to about 2 mm (water
content: 6.3%), 1 g calcium hydroxide, 1 g copper sulfide and 90 mL
methanol. After the mixture was deoxygenated twice with nitrogen under
agitation, the reaction system was filled with hydrogen to 80 atmospheres
(8 MPa), sealed and heated to 260° C. After held for 2 hours, the
system was cooled to room temperature. The pressure was only lowered by
about 4 atmospheres (no rise of pressure was observed). After the gas was
expelled, the liquid products were filtered, and the autoclave was washed
twice with a little methanol. No indication of carbonization reaction was
found in the autoclave. After the washing liquid was filtered, the filler
residue was washed twice with a little methanol and then vacuum dried.
Analysis indicated that neither organic nor elemental carbon was present
in the filter residue.

[0081] Analysis of the resultant liquid products showed that the main
organic components were single-ring aromatic compounds, multihydroxyl
compounds containing 5 and 6 carbons, and a small amount of water-soluble
polysaccharides. Further analysis indicated that among the single-ring
compounds which had a weight content of over 3% were phenol (m/e=94),
methyl phenol (m/e=108), dimethyl phenol (m/e=122), trimethyl phenol
(m/e=136), ethyl phenol (m/e=122), methoxyl phenol (m/e=124), isopropyl
phenol (m/e=136), methoxyl methyl phenol (m/e=138), vanillin (m/e=152),
with some organics at relatively lower contents. The multihydroxyl
compounds containing 5 and 6 carbons were mainly a variety of isomeric
organics having molecular weights of m/e=196, m/e=182, m/e=166, m/e=152,
m/e=136. With the aromatic compounds and the multihydroxyl compounds
considered together, the yield of small molecular organic compounds after
liquification was 89.3%.

[0082] The results show that alcohol is a good solvent, and likely,
neither carbonization nor gasification is found.

Example 5

Direct Liquification of Reed

[0083] Into a 100 mL stainless autoclave were added 5 g naturally dried
solid reed particles which had been crushed to about 2 mm (water content:
6.0%), 5 g magnesium hydroxide and 50 mL ionic liquid, i.e.
1-butyl-3-methylimidazolium tetrafluoroborate. After the mixture was
deoxygenated twice with nitrogen under agitation, the reaction system was
filled with hydrogen to 90 atmospheres (9 MPa), sealed and heated to
260° C. After held for 10 hours, the system was cooled to room
temperature. The pressure was only lowered by about 5 atmospheres. After
the gas was expelled, the liquid products were poured out, and the
autoclave was washed twice with a little water. No indication of
carbonization reaction was found in the autoclave.

[0084] Analysis of the resultant liquid products showed that the main
organic components were single-ring aromatic compounds, multihydroxyl
compounds containing 5 and 6 carbons, and a small amount of water-soluble
polysaccharides. Further analysis indicated that among the single-ring
compounds which had a weight content of over 3% were phenol (m/e=94),
methyl phenol (m/e=108), dimethyl phenol (m/e=122), trimethyl phenol
(m/e=136), ethyl phenol (m/e=122), methoxyl phenol (m/e=124), isopropyl
phenol (m/e=136), methoxyl methyl phenol (m/e=138), vanillin (m/e=152),
with some organics at relatively lower contents. The multihydroxyl
compounds containing 5 and 6 carbons were mainly a variety of isomeric
organics having molecular weights of m/e=196, m/e=182, m/e=166, m/e=152,
m/e=136. With the aromatic compounds and the multihydroxyl compounds
considered together, the yield of small molecular organic compounds after
liquification was 86.4%.

Example 6

Direct Liquification of Reed

[0085] Into a 200 mL stainless autoclave were added 5 g naturally dried
solid reed particles which had been crushed to about 2 mm (water content:
6.0%), 1 g copper chromite and 90 mL water. After the mixture was
deoxygenated twice with nitrogen under agitation, the reaction system was
filled with hydrogen to 90 atmospheres (9 MPa), sealed and heated to
260° C. After held for 6 hours, the system was cooled to room
temperature. The pressure was only lowered by about 5 atmospheres. After
the gas was expelled, the liquid products were filtered, and the
autoclave was washed twice with a little water. No indication of
carbonization reaction was found in the autoclave. After the washing
liquid was filtered, the filler residue was washed twice with a little
water and then vacuum dried. Analysis indicated that neither organic nor
elemental carbon was present in the filter residue.

Analysis of the resultant liquid products showed that the main organic
components were single-ring aromatic compounds, multihydroxyl compounds
containing 5 and 6 carbons, and a small amount of water-soluble
polysaccharides. Further analysis indicated that among the single-ring
compounds which had a weight content of over 3% were phenol (m/e=94),
methyl phenol (m/e=108), dimethyl phenol (m/e=122), trimethyl phenol
(m/e=136), ethyl phenol (m/e=122), methoxyl phenol (m/e=124), isopropyl
phenol (m/e=136), methoxyl methyl phenol (m/e=138), vanillin (m/e=152),
with some organics at relatively lower contents. The multihydroxyl
compounds containing 5 and 6 carbons were mainly a variety of isomeric
organics having molecular weights of m/e=196, m/e=182, m/e=166, m/e=152,
m/e=136. With the aromatic compounds and the multihydroxyl compounds
considered together, the yield of small molecular organic compounds after
liquification was 90.1%.

Example 7

Direct Liquification of Fresh Reed

[0086] Fresh reed was crushed by an disintegrator into a slurry containing
28% water (weight content), from which 30 g was taken and added into a 60
mL stainless autoclave together with 3 g sodium hydroxide and 300 mg
ruthenium oxide. After the mixture was deoxygenated twice with nitrogen
under agitation, the reaction system was filled with hydrogen to 100
atmospheres (10 MPa), sealed and heated to 230° C. After held for
2 hours, the system was cooled to room temperature. The pressure was only
lowered by about 5 atmospheres. After the gas was expelled, the liquid
products were filtered, and the autoclave was washed twice with a little
1% aqueous solution of sodium hydroxide. No indication of carbonization
reaction was found in the autoclave. After the washing liquid was
filtered, the filler residue was washed twice with a little 1% aqueous
solution of sodium hydroxide and then vacuum dried. Analysis indicated
that neither organic nor elemental carbon was present in the filter
residue.

[0087] Analysis of the resultant liquid products showed that the main
organic components were single-ring aromatic compounds, multihydroxyl
compounds containing 5 and 6 carbons, and a small amount of water-soluble
polysaccharides. Further analysis indicated that among the single-ring
compounds which had a weight content of over 3% were phenol (m/e=94),
methyl phenol (m/e=108), dimethyl phenol (m/e=122), trimethyl phenol
(m/e=136), ethyl phenol (m/e=122), methoxyl phenol (m/e=124), isopropyl
phenol (m/e=136), methoxyl methyl phenol (m/e=138), vanillin (m/e=152),
with some organics at relatively lower contents. The multihydroxyl
compounds containing 5 and 6 carbons were mainly a variety of isomeric
organics having molecular weights of m/e=196, m/e=182, m/e=166, m/e=152,
m/e=136. With the aromatic compounds and the multihydroxyl compounds
considered together, the yield of small molecular organic compounds after
liquification was 96.1%.

[0088] The results show that, just like the case of dry reed, the
liquification reactions of fresh reed are not impacted, and the
distribution of the products is quite similar to that for dry reed.

Example 8

Direct Liquification of Bamboo

[0089] Into a 200 mL stainless autoclave were added 10 g naturally dried
bamboo particles which had been crushed to about 2 mm (water content:
5.3%), 2 g copper chromite and 90 mL 6% aqueous solution of sodium
hydroxide after they were mixed homogenously. After the mixture was
deoxygenated twice with nitrogen under agitation, the reaction system was
filled with hydrogen to 100 atmospheres (10 MPa), sealed and heated to
220° C. After held for 1.5 hours, the system was cooled to room
temperature. The pressure was only lowered by about 5 atmospheres. After
the gas was expelled, the liquid products were filtered, and the
autoclave was washed twice with a little 1% aqueous solution of sodium
hydroxide. No indication of carbonization reaction was found in the
autoclave. After the washing liquid was filtered, the filler residue was
washed twice with a little 1% aqueous solution of sodium hydroxide and
then vacuum dried. Analysis indicated that neither organic nor elemental
carbon was present in the filter residue.

Analysis of the resultant liquid products showed that the main organic
components were single-ring aromatic compounds, multihydroxyl compounds
containing 5 and 6 carbons, and a small amount of water-soluble
polysaccharides. Further analysis indicated that among the single-ring
compounds which had a weight content of over 3% were phenol (m/e=94),
methyl phenol (m/e=108), dimethyl phenol (m/e=122), trimethyl phenol
(m/e=136), ethyl phenol (m/e=122), methoxyl phenol (m/e=124), isopropyl
phenol (m/e=136), methoxyl methyl phenol (m/e=138), vanillin (m/e=152),
with some organics at relatively lower contents. The multihydroxyl
compounds containing 5 and 6 carbons were mainly a variety of isomeric
organics having molecular weights of m/e=196, m/e=182, m/e=166, m/e=152,
m/e=136. With the aromatic compounds and the multihydroxyl compounds
considered together, the yield of small molecular organic compounds after
liquification was 86.3%.

Example 9

Direct Liquification of Cow Dunq

[0090] Into a 30 mL stainless autoclave were added 10 g naturally dried
solid cow dung particles (water content: 6.0%) and 0.2 g potassium
hydroxide. After the mixture was deoxygenated twice with nitrogen, the
reaction system was filled with nitrogen to 2 atmospheres (1 MPa), sealed
and heated to 580° C. After held for 5 minutes, the system was
cooled to room temperature. After the gas was expelled, the liquid
products were poured out, and the autoclave was washed twice with a
little water. No indication of carbonization reaction was found in the
autoclave. Analysis of the resultant liquid products showed that the main
organic components were single-ring aromatic compounds, and those which
had a weight content of over 3% were phenol (m/e=94), methyl phenol
(m/e=108), dimethyl phenol (m/e=122), trimethyl phenol (m/e=136), ethyl
phenol (m/e=122), methoxyl phenol (m/e=124), isopropyl phenol (m/e=136),
methoxyl methyl phenol (m/e=138), vanillin (m/e=152), with some organics
at relatively lower contents. The yield of small molecular organic
compounds after liquification was 71.4%.

Examples 10-11

Direct Liquification of Bean Stalk (Dry) and Corn Stalk (Dry)

[0091] The process as described in Example 9 was carried out, except that
the cow dung in Example 9 was replaced with bean stalk (Example 10) or
corn stalk (Example 11). The results were shown in the following table.

[0092] The starting materials of cellulosic biomass, catalysts selected,
liquification conditions and yields for Examples 1-11 were reported in
the following table.

[0093] All of the documents mentioned in the invention are incorporated
herein by reference, as if each of them were cited as reference
independently. In addition, it is to be understood that, after reading
the foregoing teachings of the invention, various changes or
modifications will be apparent to those skilled in the art. These
equivalents are considered to fall in the scope of the application
defined by the appended claims.